US7497971B2 - Mixtures of fluorescent whitening agents - Google Patents
Mixtures of fluorescent whitening agents Download PDFInfo
- Publication number
- US7497971B2 US7497971B2 US10/537,062 US53706205A US7497971B2 US 7497971 B2 US7497971 B2 US 7497971B2 US 53706205 A US53706205 A US 53706205A US 7497971 B2 US7497971 B2 US 7497971B2
- Authority
- US
- United States
- Prior art keywords
- formula
- weight
- fluorescent whitening
- compound
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related, expires
Links
- 0 *C.C1=CC=C2OC(C/C3=N/C4=C(C=CC=C4)O3)=NC2=C1.[1*]C Chemical compound *C.C1=CC=C2OC(C/C3=N/C4=C(C=CC=C4)O3)=NC2=C1.[1*]C 0.000 description 4
- SYYSAULJZBYGLB-VJJINTEWSA-N C/C=C/C.CC1=CC=C(C)C2=CC=CC=C12.CC1=CC=C(C)S1 Chemical compound C/C=C/C.CC1=CC=C(C)C2=CC=CC=C12.CC1=CC=C(C)S1 SYYSAULJZBYGLB-VJJINTEWSA-N 0.000 description 2
- DZSGVWMCABCYDJ-DUWBUDFISA-N CC1=CC=C(/C=C/C2=CC=C(/C=C/C3=CC=CC=C3C#N)C=C2)C=C1 Chemical compound CC1=CC=C(/C=C/C2=CC=C(/C=C/C3=CC=CC=C3C#N)C=C2)C=C1 DZSGVWMCABCYDJ-DUWBUDFISA-N 0.000 description 2
- IIJZXQVVBKTUBA-ILHSMLOTSA-N C1=CC=C2OC(C3=CC=C(/C4=N/C5=C(C=CC=C5)O4)S3)=NC2=C1.CC1=CC=C2OC(/C=C/C3=N/C4=C(C=CC(C)=C4)O3)=NC2=C1 Chemical compound C1=CC=C2OC(C3=CC=C(/C4=N/C5=C(C=CC=C5)O4)S3)=NC2=C1.CC1=CC=C2OC(/C=C/C3=N/C4=C(C=CC(C)=C4)O3)=NC2=C1 IIJZXQVVBKTUBA-ILHSMLOTSA-N 0.000 description 1
- TWIXRCBDGPKUSU-JKVWCLTQSA-N C1=CC=C2OC(C3=CC=C(C4=NC5=C(C=CC=C5)O4)S3)=NC2=C1.CC1=CC=C2OC(/C=C/C3=NC4=C(C=CC(C)=C4)O3)=NC2=C1.N#CC1=CC=C(/C=C/C2=CC=C(/C=C/C3=CC=CC=C3C#N)C=C2)C=C1 Chemical compound C1=CC=C2OC(C3=CC=C(C4=NC5=C(C=CC=C5)O4)S3)=NC2=C1.CC1=CC=C2OC(/C=C/C3=NC4=C(C=CC(C)=C4)O3)=NC2=C1.N#CC1=CC=C(/C=C/C2=CC=C(/C=C/C3=CC=CC=C3C#N)C=C2)C=C1 TWIXRCBDGPKUSU-JKVWCLTQSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/60—Optical bleaching or brightening
- D06L4/614—Optical bleaching or brightening in aqueous solvents
- D06L4/636—Optical bleaching or brightening in aqueous solvents with disperse brighteners
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/60—Optical bleaching or brightening
- D06L4/65—Optical bleaching or brightening with mixtures of optical brighteners
Definitions
- the present invention relates to mixtures of fluorescent whitening agents (FWAs) based on dicyano-1,4-bis-styrylbenzenes and bisbenzoxazoles.
- FWAs fluorescent whitening agents
- Fluorescent whitening agents are often used in the form of mixtures of two or more components, since such mixtures may exhibit a higher degree of whiteness than that of the sum of the individual components alone.
- GB 2200660 describes mixtures of 2,3′-, 2,4′- and 4,4′-dicyano-1,4-bis-styrylbenzenes, although the composition is restricted by the method of preparation, whilst U.S. Pat. No. 5,695,686 describes similar asymmetric mixtures containing further isomers again due to the process of preparation.
- R 1 denotes hydrogen, C 1 -C 6 alkyl, C 5 -C 14 aryl or C 6 -C 24 aralkyl and X is a bivalent radical of formula (3), (4) or (5)
- mixtures comprising 13 to 17% by weight, more preferably 14 to 16% by weight, of the compound of formula (1) and 83 to 87% by weight, more preferably 84 to 86% by weight, of the compound of formula (2) are of particular interest.
- the compounds of formulae (1) and (2) are well-known FWAs and commercially available or can be prepared according to well-known methods.
- C 1 -C 6 alkyl as R 1 includes for example methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, amyl, tert-amyl(1,1-dimethylpropyl)n-pentyl, neopentyl, and n-hexyl.
- C 5 -C 14 aryl examples are phenyl, tolyl, mesityl, isityl, xylyl, naphthyl, anthryl and phenanthryl.
- C 6 -C 24 aralkyl as R 1 includes for example benzyl, 2-phenylethyl, diphenylmethyl, naphthylmethyl and 2-naphthylethyl.
- the mixtures according to the invention contain a compound of formula (1a)
- R 1 and X are as defined above.
- Preferred compounds of formula (2a) are those wherein R 1 denotes hydrogen or C 1 -C 6 alkyl.
- mixtures according to the invention contain 13 to 17% by weight, most preferably 14 to 16% by weight, of a compound of formula (1a) and 83 to 87% by weight, most preferably 84 to 86% by weight, of a compound of formula (2c).
- compositions of the compounds of the formulae (1) and (2) for whitening synthetic fibres, in particular polyester fibres, said compositions containing a mixture comprising 5 to 60% by weight of a compound of formula 1 and 40 to 95% of a compound of formula (2).
- the individual components can be processed to the commercial form by dispersing them in a liquid medium, preferably water. This can be done by dispersing the individual components and then combining the dispersions so obtained. However, it is also possible to mix the individual components together in substance and then to disperse them jointly.
- the dispersing operation is carried out in a conventional manner in ball mills, colloid mills, bead mills or the like.
- the present invention thus further provides brightener compositions containing water and, in each case based on the weight of the formulation, from 3 to 25% by weight, preferably from 10 to 20% by weight of the above defined fluorescent whitening agent mixture and also 0 to 60%, preferably 5 to 50% by weight, of auxiliaries.
- Suitable auxiliaries include, for example, dispersing and wetting agents, antifreezes, antifoams, thickeners/stabilizers and biocides.
- anionic dispersants are condensates of aromatic sulfonic acids as well as ligninsulfonates, alkyl aryl sulfonates, alkyl diphenyl oxide sulfonates, sulfates or phosphates of ethoxylated alkyl phenols, di- or tristyrylphenols.
- non-ionionic dispersants are ethylene oxide adducts with fatty alcohols, higher fatty acids, alkyl phenols, sorbitol esters, di- and tristyrylphenol; copolymers of ethylene oxide and propylene oxide or ethylenediamine ethylene oxide/propylene oxide adducts.
- thickeners/stabilizers are copolymers of N-vinylpyrrolidone with 3-vinylpropionic acid, polyvinylalcohols or non-ionic/anionic polysaccharides.
- mixtures of this invention and the compositions containing them are suitable for whitening textile materials made from synthetic fibres, in particular, those made from linear polyesters.
- these mixtures and compositions can also be used for whitening blends that contain linear polyesters.
- the mixtures of this invention are applied by the methods normally employed for the application of fluorescent whitening agents, for example, by the exhaust dyeing process in dyeing machines or by pad-thermofixation.
- the treatment is conveniently effected in an aqueous medium in which the compounds are present in finely particulate form as suspensions, microdispersions or, as the case may be, solutions. If appropriate, dispersants, stabilisers, wetting agents and other assistants can be added during the treatment.
- the treatment is normally carried out in the temperature range from about 20° C. to 140° C., preferably 110 to 130° C., for example, at the boiling temperature of the bath or in the proximity thereof.
- the thermofixing is preferably carried out at a temperature of between 170 and 200° C.
- the mixtures according to the invention provide a blue shade without the addition of shading dyes.
- the materials treated with the mixtures according to the invention exhibit a high lightfastness as well as a high whiteness level and excellent brilliancy.
- Polyester fabrics are treated with mixtures containing the compounds of formulae (1a) and (2b) or (2c), respectively, and analysed with respect to degree of whiteness according to Ganz, lightfastness according to ISO 105-B02, tint value TV according to Ganz-Griesser, lightness L* according to the CIELAB system and brightness B (D65) according to ISO 2470.
- the results are summarised in Tables 1a, 1b, 2a and 2b.
- a polyester fabric (prescoured, heat-set at 195° C., 165 g/m 2 ) is treated, in a dyeing apparatus, at room temperature and at a liquor ratio of 1:20, with an aqueous bath containing a mixture of the optical brightening agents of formula (1a) and (2c) in the ratios given in Table 1, in finely dispersed form and in the presence of 1 g/l of a fatty alcohol polyglycol ether as dispersing agent.
- the temperature is raised from room temperature to 130° C. over 30 minutes, held for a further 30 minutes at this temperature and subsequently cooled to 40° C. during 15 minutes.
- the textile material is then rinsed for 30 seconds under running water and dried at 70° C.
- a polyester fabric (prescoured, heat-set at 195° C., 165 g/m 2 ) is treated at room temperature by the pad-bake process with an aqueous liquor containing a mixture of the optical brightening agents of formula (1a) and (2c) in the ratios given in Table 1, in dispersed form and in the presence of 1 g/l of an alkali salt of a sulfonated dicarboxylic acid alkyl ester.
- the liquor pick-up is 50%.
- the fabric sample is dried for 30 minutes at 70° C. and then thermofixed during 30 seconds at 180° C.
- a polyester fabric (prescoured, heat-set at 195° C., 165 g/m 2 ) is treated by the exhaust process and by the pad-batch process, respectively, as described in Example 1.
- the Ganz whiteness, tint value, lightness and brightness of the treated samples are given in Tables 2a and 2b.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Detergent Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Coloring (AREA)
- Paper (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02406084 | 2002-12-10 | ||
EP020406084.0 | 2002-12-10 | ||
PCT/EP2003/050913 WO2004053221A1 (en) | 2002-12-10 | 2003-12-01 | Mixtures of fluorescent whitening agents |
Publications (2)
Publication Number | Publication Date |
---|---|
US20060048309A1 US20060048309A1 (en) | 2006-03-09 |
US7497971B2 true US7497971B2 (en) | 2009-03-03 |
Family
ID=32479850
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/537,062 Expired - Fee Related US7497971B2 (en) | 2002-12-10 | 2003-12-01 | Mixtures of fluorescent whitening agents |
Country Status (13)
Country | Link |
---|---|
US (1) | US7497971B2 (ja) |
EP (1) | EP1570122B1 (ja) |
JP (1) | JP4580241B2 (ja) |
CN (1) | CN100338296C (ja) |
AT (1) | ATE413489T1 (ja) |
AU (1) | AU2003298335A1 (ja) |
BR (1) | BR0317151A (ja) |
DE (1) | DE60324588D1 (ja) |
ES (1) | ES2316862T3 (ja) |
MX (1) | MXPA05005771A (ja) |
TW (1) | TW200413596A (ja) |
WO (1) | WO2004053221A1 (ja) |
ZA (1) | ZA200503644B (ja) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005019189A1 (en) * | 2003-08-21 | 2005-03-03 | Ciba Specialty Chemicals Holding Inc. | Optical brighteners |
ES2626605T3 (es) * | 2011-01-20 | 2017-07-25 | Huntsman Advanced Materials (Switzerland) Gmbh | Formulaciones de agentes blanqueadores fluorescentes en forma dispersada |
CN105019221A (zh) * | 2014-08-20 | 2015-11-04 | 太仓市璜泾太华化纤助剂厂 | 一种提高化纤白度的化纤助剂 |
GB2551487A (en) * | 2016-06-15 | 2017-12-27 | Reckitt Benckiser Vanish Bv | Composition |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4008166A (en) | 1973-09-05 | 1977-02-15 | Ciba-Geigy Corporation | Optically brightening with a synergistic mixture |
US4105399A (en) | 1973-09-05 | 1978-08-08 | Ciba-Geigy Corporation | Optically brightening with a synergistic mixture |
EP0030917A2 (de) | 1979-12-13 | 1981-06-24 | Ciba-Geigy Ag | Optische Aufheller aus Bis-styrylbenzolverbindungen, Verfahren zu deren Herstellung und deren Verwendung |
DE3313332A1 (de) | 1983-04-13 | 1984-10-18 | Hoechst Ag, 6230 Frankfurt | Mischungen von optischen aufhellern zum aufhellen von polyvinylchlorid |
EP0240461A1 (de) | 1986-04-02 | 1987-10-07 | Ciba-Geigy Ag | Mischungen von optischen Aufhellern |
US5051111A (en) * | 1987-11-27 | 1991-09-24 | Ciba-Geigy Corporation | Whitener dispersion |
US5053055A (en) * | 1987-11-27 | 1991-10-01 | Ciba-Geigy Corporation | Whitener dispersion |
WO1999005356A1 (de) | 1997-07-25 | 1999-02-04 | Clariant Gmbh | Mischungen von optischen aufhellern |
US20030192137A1 (en) | 2000-07-20 | 2003-10-16 | Fabienne Cuesta | Method for the fluorescent whitening of cotton |
US6719922B1 (en) * | 1999-09-06 | 2004-04-13 | Ciba Specialty Chemicals Corporation | Mixtures of fluorescent whitening agents |
US20050106114A1 (en) | 2002-02-18 | 2005-05-19 | Georges Metzger | Process for improving the sun protection factor of cellulosic fibre material |
US20050120490A1 (en) | 2002-03-18 | 2005-06-09 | Georges Metzger | Process for improving the sun protection factor of cellulosic fibre material |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2807497A1 (de) * | 1978-02-22 | 1979-08-23 | Bayer Ag | Distyryl-verbindungen |
DE2929687A1 (de) * | 1979-07-21 | 1981-02-12 | Hoechst Ag | Mischungen von optischen aufhellern |
CH650792A5 (en) * | 1979-12-13 | 1985-08-15 | Ciba Geigy Ag | Optical brighteners from bisstyrylbenzene compounds and preparation thereof |
DE10219993A1 (de) * | 2002-05-03 | 2003-11-20 | Basf Ag | Verfahren zum Aufhellen von textilen Materialien |
-
2003
- 2003-12-01 AU AU2003298335A patent/AU2003298335A1/en not_active Abandoned
- 2003-12-01 WO PCT/EP2003/050913 patent/WO2004053221A1/en active Application Filing
- 2003-12-01 US US10/537,062 patent/US7497971B2/en not_active Expired - Fee Related
- 2003-12-01 JP JP2004558099A patent/JP4580241B2/ja not_active Expired - Fee Related
- 2003-12-01 BR BR0317151-5A patent/BR0317151A/pt not_active Application Discontinuation
- 2003-12-01 EP EP03796069A patent/EP1570122B1/en not_active Expired - Lifetime
- 2003-12-01 CN CNB2003801055478A patent/CN100338296C/zh not_active Expired - Fee Related
- 2003-12-01 ES ES03796069T patent/ES2316862T3/es not_active Expired - Lifetime
- 2003-12-01 AT AT03796069T patent/ATE413489T1/de not_active IP Right Cessation
- 2003-12-01 MX MXPA05005771A patent/MXPA05005771A/es active IP Right Grant
- 2003-12-01 DE DE60324588T patent/DE60324588D1/de not_active Expired - Lifetime
- 2003-12-08 TW TW092134543A patent/TW200413596A/zh unknown
-
2005
- 2005-05-06 ZA ZA200503644A patent/ZA200503644B/en unknown
Patent Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4008166A (en) | 1973-09-05 | 1977-02-15 | Ciba-Geigy Corporation | Optically brightening with a synergistic mixture |
US4105399A (en) | 1973-09-05 | 1978-08-08 | Ciba-Geigy Corporation | Optically brightening with a synergistic mixture |
EP0030917A2 (de) | 1979-12-13 | 1981-06-24 | Ciba-Geigy Ag | Optische Aufheller aus Bis-styrylbenzolverbindungen, Verfahren zu deren Herstellung und deren Verwendung |
US4778623A (en) | 1979-12-13 | 1988-10-18 | Ciba-Geigy Corporation | Fluorescent brighteners consisting of bis-styrylbenzene compounds, a process for their preparation and their use |
US4785128A (en) | 1979-12-13 | 1988-11-15 | Ciba-Geigy Corporation | Process for the preparation of bis-styrylbenzenes |
US5001253A (en) | 1979-12-13 | 1991-03-19 | Ciba-Geigy Corporation | Fluorescent brighteners consisting of bis-styrylbenzene compounds, a process for their preparation and their use |
DE3313332A1 (de) | 1983-04-13 | 1984-10-18 | Hoechst Ag, 6230 Frankfurt | Mischungen von optischen aufhellern zum aufhellen von polyvinylchlorid |
EP0240461A1 (de) | 1986-04-02 | 1987-10-07 | Ciba-Geigy Ag | Mischungen von optischen Aufhellern |
US5051111A (en) * | 1987-11-27 | 1991-09-24 | Ciba-Geigy Corporation | Whitener dispersion |
US5053055A (en) * | 1987-11-27 | 1991-10-01 | Ciba-Geigy Corporation | Whitener dispersion |
WO1999005356A1 (de) | 1997-07-25 | 1999-02-04 | Clariant Gmbh | Mischungen von optischen aufhellern |
US6120704A (en) * | 1997-07-25 | 2000-09-19 | Clariant Gmbh | Mixtures of optical brighteners |
US6719922B1 (en) * | 1999-09-06 | 2004-04-13 | Ciba Specialty Chemicals Corporation | Mixtures of fluorescent whitening agents |
US20030192137A1 (en) | 2000-07-20 | 2003-10-16 | Fabienne Cuesta | Method for the fluorescent whitening of cotton |
US20050106114A1 (en) | 2002-02-18 | 2005-05-19 | Georges Metzger | Process for improving the sun protection factor of cellulosic fibre material |
US20050120490A1 (en) | 2002-03-18 | 2005-06-09 | Georges Metzger | Process for improving the sun protection factor of cellulosic fibre material |
Also Published As
Publication number | Publication date |
---|---|
EP1570122B1 (en) | 2008-11-05 |
CN1723311A (zh) | 2006-01-18 |
JP4580241B2 (ja) | 2010-11-10 |
CN100338296C (zh) | 2007-09-19 |
ZA200503644B (en) | 2006-07-26 |
WO2004053221A1 (en) | 2004-06-24 |
JP2006509087A (ja) | 2006-03-16 |
MXPA05005771A (es) | 2005-08-16 |
BR0317151A (pt) | 2005-11-01 |
AU2003298335A1 (en) | 2004-06-30 |
EP1570122A1 (en) | 2005-09-07 |
ATE413489T1 (de) | 2008-11-15 |
ES2316862T3 (es) | 2009-04-16 |
TW200413596A (en) | 2004-08-01 |
US20060048309A1 (en) | 2006-03-09 |
DE60324588D1 (de) | 2008-12-18 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: CIBA SPECIALTY CHEMICALS CORP., NEW YORK Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DONZE, JEAN-JACQUES;MEYBERGER, MARIE;MILDE, MICHAEL;AND OTHERS;REEL/FRAME:017363/0020;SIGNING DATES FROM 20050418 TO 20050425 |
|
REMI | Maintenance fee reminder mailed | ||
LAPS | Lapse for failure to pay maintenance fees | ||
STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |
|
FP | Lapsed due to failure to pay maintenance fee |
Effective date: 20130303 |